Copperable disazo dyestuffs



"ties that they withstand repeated soap washings.

United States Patent COPPERABLE DISAZO DYESTUFFS Werner Bossard, Riehen, near Basel, and Marcel Reding, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm No Drawing. Application May 1, 1953, Serial No. 352,570

Claims priority, application Switzerland May 8, 1952 8 Claims. (Cl. 260-175) The present invention concerns the production of new, metallisable disazo dyestuffs, the coppered dyeings on cellulose of which have such good wet fastness proper- The new dyestuffs, which dye in greenish-yellow shades, thus enrich the group of copperable cellulose dyestuffs which are fast to light and washing in a part of the spectrum where, up to now, the number of dyestuffs available have been insuflicient due to the high demands made upon them. They close a gap therefore, in this valuable class of dyestuffs.

Among other things U. S. Patent No. 2,515,546 shows that by coupling 1 mol of both a diazotised Z-amino-lhydroxybenzene and 2-amino-l-carboxybenzene compound with a 4.4-di-acetoacetylaminodiphenyl compound, metallisable disazo dyestuffs can be obtained, the coppered cellulose dyeings of which withstand repeated soap washings. They dye however, in somewhat reddish-yellow shades. The drawing power of previously known similar disazo dyestuffs from 2 mols of diazotised 2-amino-1-carboxybenzene compounds is inferior and such dyestuffs produce coppered cellulose dyeings the slight wet fastness properties of which do not-"withstand repeated soap washings.

It has now been found that valuable greenish-yellow to pure yellow copperable disazo dyestuffs can be obtained if 1 mol of an unsulphonated 4.4'-di-acetoacetylaniino-diphenyl compound which can be further substituted in the 3.3'-position is coupled with 1 mol of both a diazonium compound of the general formula:

A-NH-CO-NH and 1 mol of an o-carboxy-diazonium compound of the benzene or naphthalene series, which may also be identical with the first diazonium compound. The components can be coupled in any order. In the above formula A represents a radical of the benzene or naphthalene series which is substituted by at least one acid water-solubilising group and which in addition, can contain the other substituents usual in no dyestuffs.

Apart from 4.4'-di-acetoacetylamino-diphenyl itself, derivatives thereof substituted in the 3.3'-position by low molecular alkyl and alkoxy groups or by halogen can be named as azo components usable according to the present invention. Of these, 3.3-dimethoxy-414'-diaminodiphenyl produces dyestuffs which have excellent wet fastness properties but are of a more reddish shade, and 3.3' dichloro-4.4-diaminodiphenyl and 3.3-dimethyl-4.4-diaminodiphenyl produce the most interesting disazo dyestuffs according to this invention in regard to shade and properties.

The characteristic diazo components corresponding to the above formula can be produced from 1 mol of 5- arnino-Z-acetylaminobenzene-l-carboxylicacid and 1 mol of a primary amino compound of the benzene and naphthalene series which corresponds to A, and which hce contains at least one sulphonic acid or carboxyl group as acid water-solubilising group and in addition can be further substituted by the halogen, alkyl, alkoxyl, hydroxyl groups or heterocyclic radicals usual in azo dyestuffs. The diazo components are produced by treating the aqueous solution of the alkali salts either with phosgene until the primary amino groups have disappeared or by acylating first one of the components, preferably that corresponding to A, with a chloroformic acid phenol ester and treating the other component in aqueous solution of the alkali salts with the arylcarbamic acid phenol ester so obtained until the unsymmetrical urea derivative is formed with splitting off of phenol, whereupon the acetylamino group is saponified under mild conditions. The symmetrical urea derivatives also obtained by the first method can be removed after saponification of the acetylamino groups with diluted mineral acids because of the different solubility of the alkali salts in water.

Amino compounds of the benzene and naphthalene series which correspond to A and are usable are, e. g. 3- or 4-aminobenzene-l-sulphonic acids or -carboxylic acids, 2-methoxy-, 2-chloroor 2-methyl-5-aminoben zene-l-sulphonic acids, 4-chloroor 4-methyl-5-aminobenzene-l-sulphonic acids, 5-amino-2-hydroxybenzenel-car'boxylic acid, 5-amino-3-methylor -3-sulpho-2-hydroXy-benzene-l-carboxylic acids, 'l-aminonaphthalene- 4-sulphonic acid, 2-aminonaphthalene-4.8- or -6.8-disulsulphonic acids, 2 (4 aminophenyl) 6 methylbenzothiazole-S- or -7-sulfonic acids.

Either the same or a different o-aminocarboxylic acid of the benzene and naphthalene series can be used as second diazo component, in the latter case, e. g. 2- aminobenzene-l-carboxylic acid, 2-aminobenzene-L4- or LS-dicarboxylic acid, Z-amino-1-carboxybenzene-4- or -5-sulphonic acid and the corresponding sulphonic acid amides, -dimethylamides, -ethanolamides etc., l-aminonaphthalene-Z-carboxylic acid, 2-aminonaphthalene-3- carboxylic acid, in particular however S-acylamino-Z- amino-benzoic acids such as 5-acetylamino-, S-carbomethoXyamino-, 5-carbethoXyamino-, S-carbomethoxyethoxyamino-2-aminobenzoic acid, because these have a particularly favourable effect on the drawing power and fastness properties of the dyestuffs produced therewith according to the present invention.

The new, characteristic diazo components are diazotised most advantageously according to the indirect method by the dropwise addition of an aqueous solution of their alkali salts which also contains the necessary amount of alkali nitrite in solution, into diluted mineral acid in the cold.

The coupling is performed in a neutral to alkaline solution or suspension. To produce unsymmetricaldisazo dyestuffs the process is performed in steps and it is of advantage to couple "that diazo component in the first step which will lead to a more easily Water-solubl monoazo dyestutf intermediate product.

The disazo dyestuffs according to the present invention obtained by salting out from the coupling solution, filtering under suction and drying, are in the form of yellow powders which dissolve well in hot water, if necessary after mixing with inorganic salts having an alkaline reaction such as sodium phosphates or polyphosphates. They dye cellulose fibres direct according to the usual methods in greenish-yellow shades.

The disazo dyestuffs according to the present invention can be coppered in the dyebath or in a fresh bath in a neutral or Weakly acid medium with the usual copper salts such as, e. g. copper sulphate or copper acetate. If desired, copper compounds which are stable to alkalies can also be used such as,--for example, those obtained by reacting copper sulphate with sodium tartrate in a soda- .coppering, it dyes them in pure greenish-yellow shades.

alkaline bath. The shade is only slightly altered on is a yellow powder which after being mixed with an after-treating the cellulose dyeing with agents giving ofl? equal quantity of sodium pyrophosphate dissolves in copper but the wet fastness and light fastness properties water and in concentrated sulphuric acid with a yellow are considerably improved. colour. Natural or regenerated cellulose fibres are dyed The following examples illustrate the invention within clear, greenish-yellow shades which, on being treated out limiting it in any way. Where not otherwise stated, with copper salts according to the usual methods, only the parts are given as parts by weight and the temperachange slightly. The dyeings have excellent wet and tures are in degrees centigrade. The relationship of parts light fastness properties. by weight to parts by volume is as that of kilogrammes If in thi example, the 35.1 parts of 4-aminodiphenyl to litres. urea-3-carboxylic acid-4-sulphonic acid is replaced by Example 1 an equal number of parts of 4-aminodiphenyl urea-3- t 'd-3-sul honic acid 43.1 parts of 4-amino- 70.2 arts of 4-am1nod1pheny1urea-3-carboxyl1c acidcilrbokyhc acl P I 3'-sulph t )nic acid and 16 parts of, caustic soda are disdiphenyl urea3fcarbo7iyhc ac1d'2 'dlsulphomc and, solved in 700 parts of water, mixed with 13.8 parts of 1 2 or 4 F f P 39 sodium nitrite and diazotised by the quick addition of 5 czfrboxyhc F- P acld, 38-55 Harts Q 72 parts of concentrated hydrochloric acid at 510. 4 I 'f P f 12 parts of sodium bicarbonate are sprinkled on the Phonic acld, P 015,2 F YP P lemon yellow suspension f the diazonium compound yl urea-3-carboxyl1c acid-6 -sulphon1c acid, 41.1 parts of a d a solution of 35.2 arts of 4.4'-diacetoacet lamino- 4'amino'4"hydroxydiphenyl urea'3-3"dlcafboxylic li l diphenyl and 8 par is of caustic soda in 5 00 par 5"sulphonic P l P Y Y of water are added. After 12 hours the thick suspenpilenyl Y P i of Sion is slowly heated to (calculated on the diphenyl urea-3.3- or -.a.4 -dicarboxylic acid, 40 1 parts volume obtained) of sodium chloride is added and the of p y p y Urea} 3'CaIbOXY1IC aclddisazo dyestuff of the formula: 4'-sulphonic acid, 48.1 parts of 4-am1nophenyl-1.1'-naph- CH! H slOsH COOH I COOH 803B which precipitates is filtered ofi. When dry the dyestufi' hyl ul'ea-3-cafboXylic acid'ygfldisulpholfic acid,

is a yellow powder which dissolves in water and in conparts of 4-aminophenyl-l.2-naphthyl urea-3-carboxylic centrated sulphuric acid with a yellow colour. It has 35 ac1d-4'.8 or -6'.8'-d1sulphon1c acid or 49.8 parts of a good drawing power onto cellulose fibres and, on aftercompound of the formula:

COOH The dyeings have excellent wet fastness properties.

I If, instead of 35.2 parts of 4.4'-diacetoacetylamino- NHCONH-ONH l.l-diphenyl, 38.0 parts of 4.4-diacetoacetylamino-3.3- 40 dimethyl-1.1-diphenyl, 42.1 parts of 4.4-diacetoacetyl- S amino-3.3'-dichloro-1.1-diphenyl or 41.2 parts of 4.4-

diacetoacetylamino-3.3-dimethoxy-1.1'-diphenyl are used,

d estutfs with similar ure shades and r0 erties are obsimilar yellow disazo dyestuffs having the same fastness y p P p tained.

properties are obtained. Example 3 Example 2 35.1 parts of 4-aminodiphenyl urea-3-carboxylic acid- 35.l parts of 4-aminodiphenyl urea-3-carboxylic acid- 3-sulphonic acid are diazotised as described in Example 4'-sulphonic acid are dissolved .in 400 parts of water 1 and coupled at 10-15 with an alkaline solution of and 8.2 parts of caustic soda, the solution is mixed with 42.1 parts of 4.4'-diacetoacetylamino-3.3'-dichloro-1.1-

'13.8 parts of sodium nitrite, cooled to 5 and 40 parts diphenyl and 20 parts of sodium carbonate. 10 parts of of concentrated hydrochloric acid are added. After some sodium bicarbonate and the diazonium compound from time the lemon yellow diazonium compound which has 26 parts of Z-aminobenzoic acid-S-sulphonic acid-[i-hyprecipitated is neutralised with 9 parts of sodium cardroxyethyl amide are added to the suspension of the bonate and added dropwise to a solution of 38 parts of 4.4'-diacetoacetylamino-3.3-dimethyl-1.1'-diphenyl in 500 monoazo dyestuff. The completely formed disazo dyestuff of the formula:

parts of water and 9 parts of caustic soda. As soon is slowly heated to 80, salted out with 15% (calculated as coupling is Completed, 20 Parts Of Sodium on the volume obtained) of sodium chloride and filtered carbonate and the diazonium compound from 19.4 parts 05 after one when dry a yellow powder is of 5'acetylammoiz'ammobenzinc acld are added The tained which dissolves in water and in concentrated sulnext day, the whole is slowly heated to 80, 10% (calculated on the volume obtained) of sodium chloride is phunc and with a yellow colour The after'coppered added, the whole is stirred for an hour at 80 and then dyeings on cellulose fibres are 3 P greenish"yellow and filtered. The disazo dyestutf obtained of the formula: have excellent fastness properties.

CH; CH: C OCH 0 I CO OH I CH3 CH: 1 I oo HOsS- Oman ONH N=NCHO ONH NHo0dH-N=N NHGO on,

COCH:

HOaSO-NHC ONH aminodiphenyl urea-3-carboxylic acid-4'-sulphonic acid and 38.0 parts of 4.4'-diacetoacetylamino-3;3 dimethyl- 1.1-diphenyl produced according to Example 2. On completion of the coupling the whole is heated slowly to: 80, 350 parts of sodium chloride are added and the precipitate is filtered off after 1 hour. The disazo dyestuff of the formula:

, NnoooonrcH ooH;

similar disazo dyestuffs with similar fastness properties 15 is a yellow powder which dissolves in water and in. conare obtained.

Example 4 36.5 parts of 4-methyl-4-aminodiphenyl urea-3-carboxylic acid-3-sulphonic.acid are dissolved in 400 parts of water and 8 parts of caustic soda at 20, mixed with 6.9 parts of sodium nitrite and then added dropwise at 510 to 36 parts of concentrated hydrochloric acid and 80 parts of water. The lemon yellow diazo suspension so obtained is neutralised with 7 parts of sodium carbonate and added dropwise to an alkaline solution of 41.2 parts of 4,4-diacetoacetylamino-3.3-dimethoxy- 1.1'-diphenyl. 'On' completion of the coupling, 10 parts of sodium bicarbonate in 200 parts of water are added and then the diazonium compound made up from 137 parts of Z-aminobenzoic acid is added. The completely formed disazo dyestuif of the formula:

S 0:3 ore-6mm ONH- is precipitated by the addition of sodium chloride at 80, filtered and dried. It is a yellow powder which dissolves in water and in concentrated sulphuric acid with a yellow colour. After-coppered it dyes cotton, staple rayon, viscose, hemp or jute fibres in pure yellow shades which have very good fastness properties.

If in this example, 19.4 parts of 4- or S-acetylamino-Z- aminobenzoic acid, 21.0 parts of 2-amino-1-carboxyphenyl-4- or -5-carbamic acid methyl ester, 22.4 parts of Z-amino-lcarboxyphenyl-4- or -5-carbarnic acid ethyl ester, 25.4 parts of 2-amino-1-carboxyphenyl-4- or -5- carbamic acid methoxyethyl ester, 26.8 parts of Z-amino- 1-carboxyplrenyl-4- or -5-carbamic acid ethoxyethyl ester, 25.2 parts of 5-succinylamino-2-aminobenzoic acid, 18.1 parts of 2-aminobenzene- 1.4 or -1.5-dicarboxylic acid, Zaminobenzoic acid-4* or -5-sulphonic acid, 21.6 parts of Z-aminobenzoic acid-5-su'lphonic acid amide, 23.0 parts of 2-aminobenzoic acid-S-sulphonic acid-methylamide, 24.4 parts of 2-arninobenzoic:acid-S-sulphonic acid-dimethylamide, 26.0 parts of Z-aminobenzoic acid- 5-sulphonic acid-B-oxethylamide, 21.5, parts of 4- or 5- methylsulphonyl-2-aminobenzoic acid, 18.7 parts of 2- aminonaphthalene-3-carboxylic acid or 18.7 parts of 1- aminonaphthalene-Z-carboxylic acid are used instead of 13.7 parts of 2-aminobenzoic acid, similar dyestuffs are obtained which have the same fastness properties.

Example 5 25.4 parts of 2-amino-1-carboxyphenyl-5-carbamic acid methoxyethyl ester are dissolved in 180 parts of water with 4.1 parts of caustic soda at mixed with parts of concentrated hydrochloric acid and diazotised at 0-5 by the addition of 6.9 parts of sodium nitrite in parts of water. The clear solution of the diazonium compound is neutralised with 6.4 parts of sodium carbonate in 60 parts of water and added to the thick liquid solution of the monoazo dyestuff from 35.1 parts of 4- COOH COCH:

centrated sulphuric acid with a yellow colour. It has excellent drawing power on to natural and regenerated cellulose fibres and, when. after-coppered, dyes them. in clear greenish-yellow shades which have excellent fastness properties.

If instead of 38.0 parts of 4.4'-diacetoacetylamino.-3.3- dimethyl-1.1'-diphenyl another of the di-acetoacetylaminodiphenyl compounds. named in example. 1 is used, similar yellow disazo dyestufls are obtained which. have similar fastness properties.

Example 6 1.0 part of the dyestulf obtained according to Example 2 is dissolved in a dyeba-th containing 3000 parts of water and 2 parts of. soda. 100 parts of cotton are entered at 4050, the bath is heated to 95 within 30 minutes, 30 parts of sodium sulphate are. added and dye- OOH;

COCH:

ing is performed for 45 minutes at this temperature. At the: end of this time the: dyebath is completely exhausted. The dyed goods are rinsed cold and after-treated at 70:? for 30 minutes in a fresh bath with 2 parts of crystallised copper sulphate in 2.000 parts of water and 2 parts of 30% acetic acid. The goods are rinsed and dried in the usual way. The cotton is. dyed. in pure greenishyellow shades which have good fastness to washing, water, perspiration and light.

What we claim is: I

l. A copperable disazo dyestuif corresponding, to the general formula:

CH1 CH: 00 OH I l o o c o A-NHC ONH- N=N( )H o ONH-D-NHC o oH-N=N- B wherein A represents an aromatic radical selected from the benzene and naphthalene series which contains an acid water-solubilising group, B represents a member selected from the group consisting of o-carboxyphenyl,

' o-monocarboxynaphthyl and o-carboxydiphenylurea radicals, and D represents an unsulphonated 4.4'-diphenyl radical.

2. A copperable disazo dyestuff corresponding to the general formula:

' CH3 CH3 COOH l l wherein A represents a sulphonated phenyl radical, B represents a member selected from the group consisting of o-carboxylphenyl, o-monocarboxynaphthyl and ocarboxydiphenylurea radicals, and D represents an unsulphonated 4.4'-diphenyl radical.

. 7 3. A 'copperable disazo dyestuff corresponding-to the general formula:

wherein A represents a sulphonated phenyl radical, D represents an unsulphonated 4.4'-dipheny1 radical and Ac represents a carboxylic acid acyl radical.

4. A copperable disazo dyestufi corresponding to the formula: v

, CH: CH8 801E GOOH GOOE SOIH I I 0 o ONES oNn-ON=N-cncONHOGNHQOQH-MN NncoNn 5. A copperable disazo dyestuif corresponding to the formula:

00: CH: COOH OH: CHI 00011 CO CO HOgSQNHC ONH- N=NCHC ONH NHCO CHN=N NHG O CH;

6. A copperable disazo dyestuff corresponding to the formula:

so.n coon c1 c1 coon coon; coon, NHC ONH N=N(.|1HOONH Nncocn-N=N so,Nn-on,-on,on

7. A copperable disazo dyestufi corresponding to the formula:

so,n coon 0on3 ocn, coon coon; I cocn. I

CH8 NHCONH N=NGHCONH NncocH-N=N 8. A coperable disazo dyestufl? corresponding to the formula:

00 OH CH: CH: COOH coon; coon HOaBGNHCONH N=N-cncoNn NHOOCHN=N nnooocnronrocn'l References Cited in the file of this patent UNITED STATES PATENTS 1,560,949 Stusser Nov. 10, 1925 2,515,546 Bossard et a1 July 18, 1950 

1. A COPPERABLE DISAZO DYESTUFF CORRESPONDING TO THE GENERAL FORMULA: 